Method for preparing carboxylate by dehydrogenating carbinol with modified amorphous copper metal catalyst

Abstract

The present invention relates to preparation process of carboxylate with modified amorphous copper alloy catalyst and alkaline mixture containing primary alcohol. The modified amorphous copper alloy catalyst prepared through a rapid cooling process is modified with one or several metal elements and non-metallic elements, including Cr, Ti, Nb, Ta, Zr, V, Mo, Si, Mo, W, etc. Under the action of the catalyst and in alkaline condition, primary alcohol is dehydrogenated to prepare carboxylate in fixed yield and high stability. The carboxylate obtained through dehydrogenating diethanolamine may be prepared into herbicide glyphosate through chemical reactions in certain conditions.

Description

technical field [0001] The present invention relates to a kind of catalyst new material is used in the method for preparing carboxylate by the dehydrogenation of primary alcohol, more particularly, the present invention relates to a kind of preparation method of novel modified amorphous copper alloy catalyst and this catalyst makes primary alcohol , especially the dehydrogenation of amino alcohols such as diethanolamine to carboxylates such as disodium iminodiacetate. Background technique [0002] Amorphous alloys are also called amorphous alloys, or metallic glasses. Their microstructures are different from crystalline metals, and they are in a thermodynamically unstable or metastable state, thus showing unique physical and chemical properties: ①Amorphous alloys Short-range order, containing a lot of coordination unsaturated atoms, rich in reactivity, so it has more surface active centers. ② Amorphous alloys have long-range disorder, and when the surface remains liquid, th...

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Problems solved by technology

[0006] Chinese patent CN1089033 discloses a method in which amorphous copper is supported on silica, and is applied to the hydrogenation of methyl formate to methanol, showing excellent results, but this method is difficult to produce on an industrial scale

In this document, the highest yield of the product iminodiacetate is 98.7%, but the amount of catalyst used is relatively large. In terms of every gram of raw material diethanolamine, about 0.2 grams of catalyst is needed, that is, the catalyst load is low, which affects the production capacity of the device.

[0010] U.S. Patent No. 5,589,000 discloses the use of precious metals such as rhodium, ruthenium, platinum, palladium, and gold to be immobilized on metals such as copper, cobalt, nickel, and cadmium. Although the activity of the catalyst has been greatly improved than before, a large amount of precious metal additives are used. , the preparation cost of the catalyst is high, and the industrial application lacks economic feasibility

[0011] Chinese patent CN1136979 discloses a method of modifying the skeleton copper catalyst to increase the catalyst load. From the disclosed results, the load of the catalyst is not much higher than before, and the catalyst accounts for about 12% of the weight of the substrate. In addition, the catalyst is stable. No evaluation, the yield is not ideal

[0012] Chinese patent CN1427812 discloses that an active phase copper is immobilized on a metal sponge carrier, and the sponge carrier is used as a supporting structure, which improves the specific surface of the catalyst, and the anti-deformation ability of the catalyst during repeated use is significantly improved, but this The activity of the catalyst is not ideal enough, and it is worse than the activity and selectivity of common Raney copper catalysts. This preparation method is difficult to prepare catalysts on an industrial scale and is not suitable for industrial applications.

[0013] China's "Chemical World" magazine, No. 11, 2001 and China's "Fine Chemical Industry" magazine, No. 10, 2001, disclosed a method for the preparation of iminodiacetic acid by the dehydrogenation of diethanolamine using an amorphous alloy. Only 16.25% of the weight of the substrate can achieve a satisfactory effect. In addition, the number of cycles of the catalyst is only more than 20. Obviously, the shortcomings of using too much catalyst and poor stability have not been solved, and the industrialization cost is too high.

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